Systems and methods for generating a conductive liquid comprising deionized water with ammonia gas dissolved therein

ABSTRACT

Systems and methods are described for dissolving ammonia gas in deionized water. The system includes a deionized water source and a gas mixing device including a first inlet for receiving ammonia gas, a second inlet for receiving a transfer gas, and a mixed gas outlet for outputting a gas mixture including the ammonia gas and the transfer gas. The system includes a contactor that receives the deionized water and the gas mixture and generates deionized water having ammonia gas dissolved therein. The system includes a sensor in fluid communication with at least one inlet of the contactor for measuring a flow rate of the deionized water, and a controller in communication with the sensor. The controller sets a flow rate of the ammonia gas based on the flow rate of the deionized water measured by the sensor, and a predetermined conductivity set point.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. Ser. No. 15/808,471, filedNov. 9, 2017, now issued as U.S. Pat. No. 10,773,221, which claims thebenefit of U.S. Provisional Application No. 62/420,953, filed Nov. 11,2016. These applications are owned by the assignee of the instantapplication and each of them is incorporated by reference herein in itsentirety.

TECHNICAL FIELD

This application relates generally to systems and methods employed inwet cleaning operations during fabrication of semiconductor devices. Inparticular, this application relates to systems and methods forgenerating and delivering deionized water with a desired concentrationof NH₃ for use in semiconductor fabrication processes.

BACKGROUND

Deionized water (“DI-water”) and ultra pure water (used interchangeablyherein) are commonly used in semiconductor device fabrication processesfor rinsing or wet cleaning operations. However, use of a substantiallynon-conductive liquid such as DI-water in semiconductor fabricationprocesses can contribute to a buildup of charge on the surface of thewafer. This is especially a problem in fabrication processes utilizingspinning wafer tools, as electroosmotic effects produced by the contactbetween the wafer and the DI water used for cleaning operations can leadto charge buildup and eventual electrostatic discharge events. Thesedischarge events can damage or even destroy structures on the wafer, orcause contaminants or undesirable particles to attach to the wafer.

Existing systems have sought to reduce charge buildup on the waferduring wet cleaning operations through the use of a conductive cleaningliquid. For example, a gas such as carbon dioxide (CO₂) can be dissolvedin the DI-water to produce carbonated deionized (“DI-CO₂”) water.

Rinsing with conductive DI-CO₂ water can avoid charge buildup on thewafer surface and allow for substantially damage-free cleaning whilemaintaining device integrity. CO₂ has the further advantage of leavingsubstantially no solid residue as a result of evaporation, which isimportant in semiconductor processing. However, DI-CO₂ water is acidicenough that it can undesirably etch away acid-sensitive materials suchas copper and cobalt which are commonly used in the back end of line(“BEOL”) stage of wafer fabrication.

Another approach uses ammonia (“NH₃”) instead of CO₂. By dissolving NH₃in DI-water, an alkaline solution with substantially lower etch ratesthan DI-CO₂ can be produced for use in wet cleaning operations.

NH₃ can be supplied as a concentrated solution or as a gas. Due to thehigh solubility of NH₃ in DI-water, use of NH₃ in its gas phase resultsin a total absorption of the NH₃ into the DI-water. However, NH₃ gas isso reactive with DI-water that there is a high risk the DI-water willflow back into the NH₃ gas supply line and into the NH₃ valves when theflow rate of NH₃ is sufficiently low. This can lead to serious controlproblems, as the flow characteristics of a valve are vastly differentbetween a gas-filled valve and the same valve filled with water. It istherefore difficult to maintain a stable flow of NH₃ gas into DI-waterunder such conditions, especially when the gas flow has to beinterrupted from time to time in the normal course of the fabricationprocess.

Some systems have sought to avoid the challenges associated withprecisely controlling the flow rate of NH₃ gas by instead using ahollow-fiber membrane system to dissolve gas that is supplied at asubstantially constant flow rate into DI-water having varying flow rates(e.g., between 1 L/min and 10 L/min). While these systems can deliver aliquid with stable conductivity under certain conditions, they do so bymaintaining a 90% or higher saturation of the liquid, requiring thatexcess NH₃ and other gases are supplied to the membrane system. This isnot only an economic disadvantage, but also requires additional effortin the treatment of the undissolved off gas leaving the system andincreases the risk in contamination of the ambient air with NH₃.

For example, NH₃ is a toxic gas and therefore special care is needed toavoid contamination of ambient air. The requirements for semiconductorfabrication are typically more restrictive regarding release of NH₃ intothe ambient air, as even NH₃ concentrations well below typicalenvironmental and health threshold limits can interfere with certainsemiconductor manufacturing and processing steps.

Another approach is to avoid using NH₃ gas altogether, and to insteaddilute a concentrated NH₃ solution into the DI-water. However, thisapproach requires a very high dilution rate that can be a factor 1000and more. Further, accurately mixing such a small quantity of a liquidinto another liquid is challenging due to the limited mixing timeprovided. Often, the limited mixing time results in fluctuations in theconcentration of the NH₃ in the liquid at the outlet to the system. Thiscan be overcome by maintaining a constant flow rate between the NH₃solution and the DI-water. However, maintaining a constant flow rate isnot preferable because of the high amount of liquid that is dischargedat times when less liquid is needed for a particular operation.Utilizing a constant flow rate results in a large amount of wastedliquid discharge, and therefore substantially increases operating costs.

In addition, a concentrated aqueous NH₃ solution absorbs CO₂ fromambient air upon contact. CO₂ can also permeate through the walls of thecontainer or tank used to store the aqueous NH₃ solution. This can leadto an increased carbonate content of the liquid over time, especially insystems that recycle a part of the supplied NH₃ solution. The carbonatecontent can interfere with the process control, as the relation betweenthe pH and the conductivity of an NH₃ solution changes based on thecarbonate content. Accordingly, systems based on the dissolution ofaqueous NH₃ require additional processing steps and components such asion exchangers to remove the carbonate and other impurities from thesupplied liquid.

Control of the concentration of the NH₃ in the DI-water, or relatedly,control of the conductivity, at the dynamically changing DI-water flowrates that are typically required for single wafer applications isdifficult. Typically, different conductivity set points are alsorequested and may take a long time to stabilize causing decreasedthroughput and therefore a higher cost of ownership. Further, due to aquadratic component between NH₃ concentration and conductivity, a muchwider range is needed for the NH₃ flow than for the DI-water flow.

Precise steady state concentration for a constant flow can theoreticallybe achieved using a feedback control to eliminate all differences overtime. However, accurate control of concentration is much morecomplicated for dynamically-changing flows of the cleaning liquid, asreal systems cannot be built with a zero volume that would behave in anideal manner. A real system has a certain volume that acts as a buffervolume during flow changes. Concentration changes are therefore oftendelayed, which leads to under dosage or concentration overshoot atchanging flow rates, which influences conductivity. Such a behavior isunwanted and needs to be restricted to small variations in conductivityin order to maintain process stability at all conditions, and in orderfor each processing chamber to operate under the same conditions.

SUMMARY

There is therefore a need for systems and methods for generating anddelivering a conductive cleaning liquid comprising DI-water with adesired concentration of NH₃ dissolved therein to prevent charge buildupon a wafer surface when used for semiconductor fabrication processessuch as wet cleaning operations. The technology described herein allowsfor precise control over the NH₃ concentration of the resulting liquideven with dynamically-changing flow rate and desired conductivitydemands during wet cleaning and other semiconductor fabricationoperations. Further, the concepts described herein provide a conductivesolution having an NH₃ concentration that results in an alkalinesolution with etch rates that are compatible with emerging semiconductorfabrication processes for treatment of advanced transistor structures.

The technology, in one aspect, features a system for dissolving ammoniagas in deionized water. The system includes a deionized water source.The system further includes a gas mixing device that includes a firstinlet in fluid communication with a first gas source for supplyingammonia gas, a second inlet in fluid communication with a second gassource for supplying a transfer gas, and a mixed gas outlet foroutputting a gas mixture including the ammonia gas and the transfer gas.The system further includes a contactor in fluid communication with thedeionized water source and the mixed gas outlet via at least one inletof the contactor. The contactor generates deionized water having ammoniagas dissolved therein. The system further includes a sensor in fluidcommunication with the at least one inlet of the contactor for measuringa flow rate of the deionized water. The system further includes acontroller in communication with the sensor. The controller isconfigured to set a flow rate of the ammonia gas supplied from the firstgas source based on the flow rate of the deionized water measured by thesensor, and a predetermined conductivity set point.

The technology can further include any of the following features. Insome embodiments, the mixed gas outlet is in fluid communication withthe deionized water source upstream of the at least one inlet of thecontactor.

In some embodiments, a static mixing device is positioned upstream ofthe at least one inlet of the contactor. The static mixing device is formixing the gas mixture output from the gas mixing device with deionizedwater output from the deionized water source.

In some embodiments, the contactor is a packed column or packed towertype contactor. In some embodiments, the at least one outlet of thecontactor includes a gas outlet for expelling an off gas from thecontactor, and a liquid outlet for outputting the deionized water havingammonia gas dissolved therein.

In some embodiments, the system further includes a fluid level sensor influid communication with the top and the bottom of the contactor. Insome embodiments, the system further includes a pressure sensor in fluidcommunication with the contactor.

In some embodiments, the system further includes a temperature sensor influid communication with one of the at least one inlet of the contactorfor measuring a temperature of the deionized water, and at least oneoutlet of the contactor for measuring a temperature of the deionizedwater having ammonia gas dissolved therein. In some embodiments, thecontroller is in communication with the temperature sensor, and thecontroller is further configured to set the flow rate of the ammonia gassupplied from the first gas source based on a temperature measured bythe temperature sensor.

In some embodiments, the controller is further configured to adjust apressure of the transfer gas output from the second gas source based onthe flow rate of the deionized water measured by the sensor. In someembodiments, the gas mixing device further includes at least one flowcontrol device in fluid communication with the first inlet of the gasmixing device. In some embodiments, the gas mixing device furtherincludes a gas injector in communication with the second inlet, and thegas injector is positioned within the gas mixing device to direct a flowof the transfer gas to an opening of an outlet of the at least one flowcontrol device of the gas mixing device.

In some embodiments, the system further includes a pump in fluidcommunication with the at least one liquid outlet of the contactor.

In some embodiments, the mixed gas outlet is in fluid communication withthe deionized water source. In some embodiments, the at least one inletof the contactor includes a liquid inlet in fluid communication with thedeionized water source, and a gas inlet in fluid communication with themixed gas outlet. In some embodiments, the gas inlet includes an exitorifice within the contactor that is positioned substantially at a meanlevel of a liquid in the contactor.

The technology, in another aspect, features a method for dissolvingammonia gas in deionized water. The method includes supplying ammoniagas to a first inlet of a gas mixing device, supplying a transfer gas toa second inlet of the gas mixing device, and supplying a gas mixturecomprising the ammonia gas and the transfer gas from the gas mixingdevice and deionized water to a contactor. The method further includesmeasuring a flow rate of the deionized water and setting a flow rate ofthe ammonia gas based on the flow rate of the deionized water and apredetermined conductivity set point. The method further includesflowing the deionized water having ammonia gas dissolved therein fromthe contactor.

The technology can further include any of the following features. Insome embodiments, the method further includes mixing the gas mixtureoutput from the gas mixing device with the deionized water upstream ofthe contactor.

In some embodiments, the contactor is a packed column or packed towertype contactor. In some embodiments, the method further includesexpelling an off gas from a gas outlet of the contactor, and flowing thedeionized water having ammonia gas dissolved therein from a liquidoutlet of the contactor. In some embodiments, the method furtherincludes sensing a fluid level of fluid in the contactor.

In some embodiments, the method further includes sensing a fluidpressure of fluid in the contactor. In some embodiments, the methodfurther includes sensing a temperature of at least one of the deionizedwater, and the deionized water having ammonia gas dissolved therein.

In some embodiments, the method further includes setting the flow rateof the ammonia gas to supply further based on the temperature. In someembodiments, the method further includes adjusting a pressure of thetransfer gas based on the flow rate of the deionized water.

In some embodiments, the method further includes controlling a flow rateof the ammonia gas supplied to the gas mixing device with at least oneflow control device. In some embodiments, the method further includessupplying the transfer gas further comprises directing a flow of thetransfer gas within the gas mixing device to an opening of an outlet ofthe at least one flow control device of the gas mixing device.

In some embodiments of the method, flowing further includes pumping thedeionized water having ammonia gas dissolved therein from the contactorvia a liquid outlet of the contactor. In some embodiments, the methodfurther includes supplying the gas mixture to the contactor furthercomprises supplying the gas mixture to a gas inlet of the contactor,wherein the gas inlet comprises an exit orifice within the contactorthat is positioned substantially at a mean level of a liquid in thecontactor.

BRIEF DESCRIPTION OF THE DRAWINGS

The advantages of the systems and methods described herein, togetherwith further advantages, may be better understood by referring to thefollowing description taken in conjunction with the accompanyingdrawings. The drawings are not necessarily to scale, emphasis insteadgenerally being placed upon illustrating the principles of the describedembodiments by way of example only.

FIG. 1 is a block diagram of a first embodiment of a system forgenerating and delivering a conductive liquid comprising DI-water withNH₃ gas dissolved therein according to embodiments of the technologydescribed herein.

FIG. 2 is a detailed block diagram of an exemplary system for generatingand delivering a conductive liquid comprising DI-water with NH₃ gasdissolved therein according to embodiments of the technology describedherein.

FIG. 3 is a block diagram of a second embodiment of a system forgenerating and delivering a conductive liquid comprising DI-water withNH₃ gas dissolved therein according to embodiments of the technologydescribed herein.

FIG. 4 is a detailed block diagram of an exemplary system for generatingand delivering a conductive liquid comprising DI-water with NH₃ gasdissolved therein according to embodiments of the technology describedherein.

FIG. 5 is a block diagram of an exemplary gas mixing device according toembodiments of the technology described herein.

FIG. 6 is a block diagram of an exemplary gas mixing device according toembodiments of the technology described herein.

FIG. 7 is a flow diagram of a method 700 for dissolving NH₃ gas inDI-water, according to embodiments of the technology described herein.

FIG. 8 is a graph of the performance of an exemplary system forgenerating and delivering a conductive liquid comprising DI-water withNH₃ gas dissolved therein, according to embodiments of the technologydescribed herein.

FIG. 9 is a graph of the performance of an exemplary system forgenerating and delivering a conductive liquid comprising DI-water withNH₃ gas dissolved therein according to embodiments of the technologydescribed herein.

DETAILED DESCRIPTION

A conductive liquid comprising NH₃ gas dissolved in DI-water can be usedin semiconductor device fabrication processes for rinsing or wetcleaning operations. For example, such a conductive liquid is commonlyused in fabrication processes employing tools such as single wafer spintools. Spin tools typically process a single wafer, one after another,in a chamber. Some higher throughput spin tools can include more thanone chamber (e.g., 2O chambers) to increase throughput. However, theoperations carried out in the individual chambers are typically notsynchronized, resulting in a randomly-changing demand for the conductiverinsing agent. Accordingly, the source of the DI-water with NH₃ gasdissolved therein must be able to maintain a stable NH₃ concentration atdynamically-changing flow rates in order to maintain the desiredconductivity of the rinsing agent.

FIG. 1 is a block diagram of a system 100 for generating and deliveringa conductive liquid comprising DI-water having a desired concentrationof NH₃ gas dissolved therein. System 100 includes gas mixing device 110,contactor 115, sensor 120 a, and sensor 120 b (collectively referred toas sensors 120). System 100 also includes a source of electrical power(not shown), and can include a control module 125.

Gas mixing device 110 can include one or more gas inlets, and can beconnected to one or more sources of gas. In the example shown in FIG. 1, a first inlet of gas mixing device 110 is in fluid communication witha source of NH₃ gas, and a second inlet of gas mixing device 110 is influid communication with a source for supplying a transfer gas. In someembodiments, the transfer gas source provides nitrogen (N₂) gas. In someembodiments, the transfer gas source provides a noble gas (e.g., argon,helium).

Gas mixing device 110 can include a plurality of variable valves, on/offvalves, filters and mass flow controllers to monitor and/or control theflow rate and amount of each gas entering and exiting gas mixing device110. The gases can be mixed within gas mixing device 110 before exitingvia an outlet. The gas mixture exiting gas mixing device 110 can bedelivered to contactor 115.

Use of gas mixing device 110 to mix NH₃ gas with a transfer gas prior tomixing the NH₃ gas with DI-water in contactor 115 provides certainadvantages. For example, mixing the NH₃ gas with a transfer gas having alow solubility in water, such as N₂, can prevent the DI-water fromsucking back into the NH₃ supply, as the transfer gas acts to separatethe DI-water from the NH₃ supply line and control valve. Further, N₂does not create a flammable mixture when mixed with NH₃ gas, thereforeavoiding safety concerns. Operation of gas mixing device 110 andadditional advantages it provides for this technology are discussed inmore detail below in reference to FIGS. 5 and 6 .

Contactor 115 typically includes at least one inlet for receiving thegas mixture from gas mixing device 110, at least one inlet for receivingDI-water from a DI-water source, at least one outlet to release or ventexcess gas (e.g., off gas), and at least one outlet to deliver therinsing agent or conductive liquid output (e.g., DI-water with NH₃ gasdissolved therein). The gas mixture can be injected, or purged into thecontactor 115. Contactor 115 can be pressurized or evacuated if desired.Contactor 115 typically allows for generation of bubble-free rinsingliquid.

System 100 can include sensors 120 for monitoring a plurality ofparameters of the various inputs to system 100 as well as the conductiveliquid output from contactor 115. In some embodiments, sensor 120 aincludes a flow meter for measuring a flow rate of the DI-water from theDI-water source, and sensor 120 b includes a temperature sensor formeasuring the temperature of the liquid output from contactor 115. Insome examples, sensor 120 b further includes a conductivity sensor formeasuring the conductivity of the liquid output from contactor 115. Insome embodiments, system 100 can include one or more other sensors formeasuring a plurality of parameters of the gases and liquids at variousstages within system 100. Such parameters can include flow rate,conductivity, temperature, and pressure.

Control module 125 can be in fluid and/or electrical communication withsensors 120 and gas mixing device 110. Control module 125 can include aprocessor, memory resources, a keypad and a display. The processor canbe for example, a microprocessor of a computer. Control module 125 canallow automatic control and/or monitoring of each valve, mass flowcontroller and sensor in system 100. In some embodiments, each valve,mass flow controller and sensor in system 100 can be controlledmanually.

In one embodiment, control module 125 can determine the required dosageof NH₃ gas to provide to gas mixing device 110, and subsequently tocontactor 115, based upon a conductivity (Kappa) set point selected by auser. For example, when NH₃ is dissolved in water (H₂O), it dissociatesresulting in the formation of an ammonium particle and a hydroxideparticle according to the following reaction:NH₃+H₂O↔NH₄ ⁺+OH⁻  EQN. 1

The dissociation is governed by the basic dissociation constant K_(b)which is a function of the water temperature. The temperature dependenceof K_(b) has been characterized, and is a predetermined quantity thatcan be stored in control module 125. For the purposes of thecalculations performed by control module 125, the concentration of NH₄ ⁺and OH⁻ can be approximated as identical. The following formula providesthe required concentration of NH₃ “cNH₃” based on the dissociationconstant K_(b) at the measured water temperature (e.g., the temperaturemeasured by sensor 120 b).cNH₃═(cNH₄ ⁺{circumflex over ( )}2+K_(b)(T)*cNH₄ ⁺)/K_(b)(T)  EQN. 2

The required flow of NH₃ gas can be calculated from the concentrationcNH₃ and DI-water flow rate measured by sensor 120 a:F_(NH3)=F_(H2O) *cNH₃  EQN. 3

The NH₄ ⁺ concentration and the OH⁻ concentration result in aconductivity equal to Kappa based on the temperature dependent specificequivalent conductivities, Lambda_(NH4)(T)+ Lambda_(OH-)(T). Thetemperature dependencies of the specific equivalent conductivities havebeen characterized, and are predetermined quantities that can be storedin control module 125. The controller is therefore able to calculateLambda_(NH4)(T)+Lambda_(OH-)(T) from the measured temperature T of theliquid output from contactor 115. The controller calculates cNH₄ ⁺ fromthe given conductivity set point Kappa from the following formula:Kappa=(Lambda_(NH4)(T)+Lambda_(OH-)(T))*cNH₄ ⁺  EQN. 4

Accordingly, control module 125 calculates the required NH₃ gas flow ina feed forward control loop, allowing system 100 to quickly react tochanges in DI-water flow rates and provide a rinsing liquid having therequired conductivity. For example, control module 125 can control oneor more valves of system 100 to adjust the flow rate of the gases and/orDI-water. In some embodiments, the calculation includes a correctionfactor that is changed very slowly based on the resulting conductivityof the liquid measured by sensor 120 b.

In some embodiments, control module 125 calculates the required flowrate or dosage of NH₃ gas to supply based on the measured temperature ofthe DI-water from the DI-water supply. In some embodiments, controlmodule 125 calculates the required flow rate or dosage of NH₃ gas tosupply based on the measured flow rate of the conductive fluid outputfrom contactor 115. In some embodiments, the calculation of the requiredflow rate or dosage of NH₃ gas to supply can be based on predeterminedassumptions about the temperature range of the liquid in the systemwithout requiring an actual temperature measurement to be obtained. Forexample, the temperature value can be based on typical environmentalconditions observed at semiconductor fabrication facilities.

FIG. 2 shows a detailed diagram of an exemplary system 200 forgenerating and delivering a conductive liquid comprising DI-water withNH₃ gas dissolved therein.

System 200 includes a gas box or gas mixing device C1 for mixing atransfer gas with NH₃ gas. Gas mixing device C1 is in fluidcommunication with a contactor B1 which is used to dissolve NH₃ gas inDI-water. The gas mixing device C1 includes a first inlet for receivingNH₃ gas, and a second inlet for receiving a transfer gas.

NH₃ gas from a first gas source is supplied to the first inlet of gasmixing device C1 by way of check valve V21 which can help avoidcontamination caused by the transfer gas flowing into the NH₃ supplylines, flow restrictor V27 which can limit the NH₃ flow in case of a gasleak in the supply, and pneumatic 2-way valve V25 which can be used toisolate the NH₃ inlet upon shutdown of system 200.

Transfer gas from a second gas source is supplied to the second inlet ofgas mixing device C1 by way of check valve V29 which can help avoidcross contamination of NH₃ gas into the transfer gas supply, andpressure regulator PRC5 (including valve V5) which is used to controlthe transfer gas pressure. Pressure relief valve V10 is positionedbetween pressure regulator PRC5 and the second inlet of gas mixingdevice C1, and can be used as a safety device to relieve pressurebuildup in the supply line before catastrophic system failure.

A gas mixture comprising NH₃ gas and the transfer gas is supplied froman outlet of gas mixing device C1 to an inlet of contactor B1 by way ofpneumatic 2-way valve V2 which can isolate gas mixing device C1 fromcontactor B1 upon shutdown and during alarm conditions, and flowrestrictor V24 which can limit liquid backflow into gas mixing device C1in the event of an unexpected pressure increase. Capacitive liquidsensor M5 is positioned near the outlet of gas mixing device C1 and actsas a safety sensor for detecting backflow of liquid. In someembodiments, capacitive liquid sensor M5 is used in conjunction withflow restrictor V24 as part of system 200's safety measures. Manual2-way valve V91 allows the mixed gas supply line to be purged duringsystem maintenance.

In the diagram of FIG. 2 , the inlet of contactor B1 for receiving thegas mixture via flow restrictor V24 is shown positioned at the bottom ofcontactor B1. The diagram reflects the typical operating mode of agas-liquid contacting device like contactor B1 in which the gas is letin at the lowest possible position into the contacting device in orderto achieve the highest possible mass transfer rate between gas andliquid. Somewhat counterintuitively, supplying the gas mixture from thispoint in contactor B1 can cause large fluctuations in the conductivityof the outlet liquid, which is undesirable.

In some embodiments, better stability of the output liquid conductivitycan be achieved by positioning the opening of the contactor inlet withincontactor B1 so that it is substantially at the mean level or height ofthe liquid in the contactor. This concept is denoted in FIG. 2 by thedashed line extending from the contactor inlet toward the center ofcontactor B1. Accordingly, even when the gas inlet of contactor B1 isphysically positioned to supply the gas mixture at or near the bottom ofcontactor B1, the exit orifice of the inlet tube internal to contactorB1 can be positioned at a height that results in better stability of theconductivity of the output liquid.

Contactor B1 can further include an outlet for expelling or venting offgas from the reactions occurring within it. For example, as the NH₃ fromthe gas mixture is dissolved into the DI-water within contactor B1, thetransfer gas can be expelled from an outlet of contactor B1. In someembodiments, a minute portion of undissolved NH₃ gas is expelled fromcontactor B1. In some embodiments, the gas outlet of contactor B1 is influid communication with an exhaust port (FIG. 2 , “Off Gas OUT”) by wayof flow restrictor V28 which can be used to effectively “throttle” thegas flow out of contactor B1, pneumatic 2-way valve V4 which can isolatethe gas outlet at shutdown, and gas filter Filter 5 which is used toprevent contaminants from the exhaust from getting into the contactor B1through its gas outlet. Further, manual 2-way valve V92 can be used as apurge valve for maintenance of system 200.

As shown in FIG. 2 , DI-water can be supplied from a DI-water source tocontactor B1 by way of pneumatic 2-way valve V3 which can isolate theDI-water inlet line at shutdown, and pneumatic 2-way valve V6 which canbe used to control the flow rate of DI-water to the liquid inlet ofcontactor B1. Further, positioner POSV6 is a pneumatic positioningdevice that can be used to control the position of valve V6. P2 is anoptional booster pump for providing sufficient water pressure to enableoperation of system 200 in locations having a DI-water supply withlimited pressure. In some embodiments, capacitive gas sensor L4 is influid communication with the DI-water supply line and is can be used todetermine whether there is liquid inside the supply line.

System 200 further includes a bypass flow path for the DI-water suppliedfrom the DI-water source. The bypass path can be used to dilute theliquid output from contactor B1. As shown in FIG. 2 , positioner POSV31is a pneumatic positioning device and can be used to control the bypassflow using continuous valve position adjustments of pneumatic 2-wayvalve V31. Flow Meter FR31 can measure the bypass flow of DI-water, andcan therefore be used to determine the required positions of the valvesin the bypass path to control the mixing ratio of DI-water having NH₃dissolved therein from contactor B1 with unmixed DI-water withoutdissolved ammonia. Measurements of the inlet DI-water pressure frompressure sensor PR3 can also be used to calculate the desired valvepositions for valves V6 and V31. In some embodiments, separator S3 ispositioned between the DI-water supply line and pressure sensor PR3.Separators such as separator S3 can be used to prevent liquid in system200 from being contaminated as a result of coming into contact with thestainless steel housings or bodies of the pressure sensors. In someembodiments, system 200 includes one or more pressure sensors that areconstructed of materials that can come into direct contact with theliquid in system 200.

In order to maintain sufficient pressure at the liquid outlet ofcontactor B1 and to facilitate a constant, stable concentration of NH₃in the output liquid, the pressure inside of contactor B1 is measuredand controlled. The pressure control acts on the DI-water flow from theDI-water source into contactor B1 or the bypass path. The pressure ofthe DI-water supplied by the DI-water source is measured by pressuresensor PR3 and the pressure inside of contactor B1 is measured bypressure sensor PR4. In some embodiments, separator S4 is positionedbetween the mixed gas supply line and pressure sensor PR4. Thesepressure measurements can be used to calculate the opening position ofvalve V6. A controller (e.g., FIG. 1 , control module 125) can be usedto control the opening position of valve V6 via positioning devicePOSV6.

The pressure control principles described herein decouple the inletDI-water pressure from the outlet liquid pressure and advantageouslymaintain a stable pressure inside of contactor B1. This is critical aspressure fluctuations in contactor B1 can result in an accumulation ofNH₃-gas in the gas supply line that does not immediately get dissolvedin the DI-water, causing a concentration drop in the conductive outputliquid. It is therefore important to maintain a stable pressure insideof contactor B1.

In some embodiments, contactor B1 is a packed column or packed towertype contactor that is filled with tower packing in order to provide asubstantial gas-liquid contact surface as the liquid flows from the topto the bottom of the contactor.

A certain liquid level can be maintained within contactor B1. Forexample, a parallel line to contactor B1 acts as level gauge, where theliquid level is measured with capacitance meter L1. In some embodiments,the liquid level is maintained substantially in the lower portion ofcontactor B1 and contactor B1 is primarily filled with gas.

Capacitive liquid sensor LAH measures the liquid level inside contactorB1 and provides an alarm if it rises too high as a safety feature tohelp avoid having liquid flow into the gas outlet of contactor B1.Capacitive gas sensor LAL also measures the liquid level insidecontactor B1 and provides an alarm if the liquid level becomes too lowas a safety feature to help avoid having gas flow into the liquid outletof contactor B1.

A conductive output liquid (e.g., DI-water with NH₃ dissolved therein)having a conductivity according to the conductivity set point selectedby the user can be output from at least one liquid outlet of contactorB1 for use in semiconductor fabrication operations (e.g., rinsingoperations, wet cleaning operations). The at least one liquid outlet ofcontactor B1 can be in fluid communication with one or more liquidoutlets of system 200 by way of filter Filter 81 which can filter theconductive output liquid, and pneumatic 2-way valve V8 which can isolatethe liquid outlet of contactor B1 upon shutdown of system 200. Pneumatic2-way valve V12 can be used as a filter drain valve for maintenance ofsystem 200, and flow restrictor V41 can be used to limit the flow ofliquid purged from filter Filter 81. Further, pneumatic 2-way valve V13can be used for de-aeration of filter Filter 81.

In some embodiments, pneumatic 2-way valve V11 can be used as a centraldrain valve and pneumatic 2-way valve V15 can be used as an additionaldrain for various maintenance purposes.

The flow rate of the conductive liquid output from contactor B1 can bemeasured with flow meter FR21. In some embodiments, FR21 is anultrasonic flow measurement device. In some embodiments, system 200includes a flow sensor for measuring the flow rate of the DI-water fromthe DI-water source. The temperature of the conductive liquid outputfrom contactor B1 can be measured at the outlet of the mixing deviceusing sensor Q1. In some embodiments, sensor Q1 is a combinedconductivity and temperature sensor, and also measures the conductivityof the liquid. In some embodiments, a separate sensor is used to measurethe conductivity of the liquid output from contactor B1. As discussedabove, the DI-water flow rate and conductive liquid temperaturemeasurements can be used to calculate the required NH₃ gas flow rate,the feed forward control that is applied in order to achieve very fastconductivity changes upon liquid flow rate changes.

Flow restrictor V43 can be used to limit the flow of liquid through orby sensor Q1, and pneumatic 2-way valve V14 can be used to isolatesensor Q1 for shutdown. In some embodiments, system 200 includescapacity liquid sensor M12 which is a liquid sensor that is positionedin or on a drop pan to detect water leaks. In some embodiments, system200 includes a drain to remove liquid that has leaked into the drop pan.In some embodiments, system 200 includes pressure sensor PR18 formeasuring the differential pressure of a cabinet housing the componentsof system 200, and PR18 generates an alarm to indicate failure modes,such as the absence of exhaust flow from system 200. In someembodiments, clean dry air CDA is supplied to system 200 for operationof the pneumatically-controlled valves. In some embodiments, system 200includes a sniffer port that can be used for detecting leaks in thecomponents of system 200.

In exemplary system 200 described above, the gas mixture is supplied toan inlet positioned at or near the bottom of the contactor. Further, thegas mixture enters the liquid in the contactor via an exit orifice ofthe inlet tube that can also be positioned at or near the bottom of thecontactor, or alternatively, can be positioned substantially at the meanlevel or height of the liquid in the contactor for better stability ofthe conductivity of the output liquid.

It was determined that the dosage point of the gas mixture to theDI-water influences the stability of the NH₃ concentration, andrelatedly the conductivity, of the liquid in response to DI-water flowchanges. The presence of stagnant “dead” volumes of gas and liquid inthe contactor act as a buffer that can delay the reaction of the systemto changes in the NH₃ flow rate. Accordingly, in some embodiments, itcan be advantageous to provide the gas mixture into the upper part ofthe contactor, or directly into the DI-water supply line upstream of theliquid inlet of the contactor.

FIG. 3 is a block diagram of a system 300 for producing and deliveringDI-water having a desired concentration of NH₃ gas dissolved in it.System 300 is substantially similar to system 100 and includes gasmixing device 110, contactor 115, sensor 120 a, and sensor 120 b(collectively referred to as sensors 120). System 300 also includes asource of electrical power (not shown), and can include a control module125.

However, as shown in FIG. 3 , the gas mixture from gas mixing device 110is supplied to the DI-water supply line upstream of the liquid inlet ofcontactor 115 instead of directly to a separate inlet of contactor 115.Further, a higher-diameter section of the DI-water supply linedownstream of where the gas mixture is connected can have mixingelements installed in it. Accordingly, by dosing the gas mixturedirectly into the DI-water supply line, a majority of the NH₃ gas can bedissolved in the DI-water prior to entering contactor 115.

Subsequently, the conductive liquid comprising DI-water and thedissolved NH₃, together with the residual undissolved gas, is fed intothe top of contactor 115. Contactor 115 can be a packed column or packedtower type contactor that is filled with tower packing in order toprovide a substantial gas-liquid contact surface. Within contactor 115,the remaining undissolved NH₃ gas is dissolved in the liquid. At thesame time, the liquid is mixed with itself resulting in a more uniformdistribution of NH₃ in the liquid. Further, the liquid and the transfergas are separated, and only the conductive liquid flows from the liquidoutlet at the bottom of contactor 115, while the transfer gas isexpelled from the off gas outlet at the top of contactor 115.

FIG. 4 shows a detailed diagram of an exemplary system 400 forgenerating and delivering a conductive liquid comprising DI-water withNH₃ gas dissolved therein.

System 400 includes a gas box or gas mixing device C1 for mixing atransfer gas with NH₃ gas. Gas mixing device C1 is in fluidcommunication with a contactor B1 which is used to dissolve NH₃ gas inDI-water. The gas mixing device C1 includes a first inlet for receivingNH₃ gas, and a second inlet for receiving a transfer gas.

NH₃ gas from a first gas source is supplied to the first inlet of gasmixing device C1 by way of manual 2-way valve V95 for allowing manualcontrol of the flow of gas as needed, flow restrictor V27 which canlimit the NH₃ flow in case of a gas leak in the supply, check valve V21which can help avoid contamination caused by the transfer gas flowinginto the NH₃ supply lines, and pneumatic 2-way valve V25 which can beused to isolate the NH₃ inlet upon shutdown of system 400. Pressuresensor PR9 can be used to measure the pressure of the NH₃ gas forcontrol and diagnostic purposes. Manual 2-way valve V93 allows thetightness of the NH₃ gas supply line to be checked after installation.

Transfer gas from a second gas source is supplied to the second inlet ofgas mixing device C1 by way of pneumatic 2-way valve V26 which canisolate the transfer gas supply line at shutdown, check valve V29 whichcan help avoid cross contamination of NH₃ gas into the transfer gassupply, pressure regulator PRC5 (including valve V5) which is used tocontrol the transfer gas pressure, and flow restrictor V36 which limitsthe transfer gas flow. For example, the flow of the transfer gas can becontrolled by maintaining a calculated pressure difference across flowrestrictor V36. This has the advantage that the flow of gas can becontrolled while simultaneously obtaining diagnostic information aboutthe gas inlet pressure. In some embodiments, pressure sensor PRC5 canalso be used as a reference pressure sensor during startup of system400.

System 400 further includes valves V32, V30, and V_(N2C1), and flowmeter FR_(N2C1) for safety reasons and to allow the system to be purgedof NH₃ gas for maintenance tasks. In some embodiments, flow meterFR_(N2C1) and valve V_(N2C1) are used to prevent a flammable mixture ofNH₃ and air from forming inside of the gas mixing device in case of aNH₃ leak. For example, they can be used to provide the transfer gas suchas N₂ in areas of insufficient gas exchange, where a NH₃ gas leak couldcause a flammable mixture with air.

A gas mixture comprising NH₃ gas and the transfer gas is supplied froman outlet of gas mixing device C1 to the DI-water supply line upstreamof contactor B1 by way of pneumatic 2-way valve V2 which can isolate gasmixing device C1 from the DI-water supply line upon shutdown and duringalarm conditions, and flow restrictor V24 which can limit liquidbackflow into gas mixing device C1 in the event of an unexpectedpressure increase. Capacitive liquid sensor M5 is positioned near theoutlet of gas mixing device C1 and acts as a safety sensor for detectingbackflow of liquid. In some embodiments, capacitive liquid sensor M5 isused in conjunction with flow restrictor V24 as part of system 200'ssafety measures. Manual 2-way valve V91 allows the mixed gas supply lineto be purged during system maintenance.

As shown in FIG. 4 , DI-water can be supplied from a DI-water source tocontactor B1 by way of pneumatic 2-way valve V3 which can isolate theDI-water inlet line at shutdown, and pneumatic 2-way valve V6 which canbe used to control the flow rate of DI-water to the liquid inlet ofcontactor B1. Further, positioner POSV6 is a pneumatic positioningdevice that can be used to control the position of valve V6. P2 is anoptional booster pump for providing sufficient pressure to enableoperation of system 400 in locations having a DI-water supply withlimited pressure.

Filters Filter 83 and Filter 82 can filter the DI-water prior to beingsupplied to the contactor to remove any particles that may have beenintroduced from the pumping action of pump P1 or from action of any ofthe valves in the supply line. Pneumatic 2-way valve V17 can be used asa filter drain valve for maintenance of system 400, and flow restrictorV44 can be used to limit the flow of liquid purged from filter Filter82. Further, pneumatic 2-way valve V18 can be used for de-aeration offilter Filter 82. Similarly, pneumatic 2-way valve V16 can be used as afilter drain valve for maintenance of system 400, and flow restrictorV45 can be used to limit the flow of liquid purged from filter Filter83. Pneumatic 2-way valve V19 can be used for de-aeration of filterFilter 83.

Measurements of the inlet DI-water pressure from pressure sensor PR3 canalso be used to calculate the desired valve positions for valve V6. Insome embodiments, separator S3 is positioned between the DI-water supplyline and pressure sensor PR3.

In some embodiments, capacitive gas sensor L4 is attached to the outersurface of the DI-water supply line and can be used to determine whetherthere is liquid inside the supply line. The flow rate of the DI-watersupply can be measured with flow meter FR21. In some embodiments, FR21is an ultrasonic flow measurement device. In some embodiments, system400 includes a flow sensor for measuring the flow rate of the conductiveliquid from a liquid outlet of the contactor.

Contactor B1 can further include an outlet for expelling off gas fromthe reactions occurring within it. For example, as the NH₃ from the gasmixture is dissolved into the DI-water within contactor B1, the transfergas can be expelled from an outlet of contactor B1. In some embodiments,a minute portion of undissolved NH₃ gas is expelled from contactor B1.In some embodiments, the gas outlet of contactor B1 is in fluidcommunication with an exhaust port (FIG. 4 , “Off Gas OUT”) by way offlow restrictor V28 which can be used to effectively “throttle” the gasflow out of contactor B1, pneumatic 2-way valve V4 which can isolate thegas outlet at shutdown, and gas filter Filter 5 which is used to preventcontaminants from the exhaust from getting into the contactor B1 throughits gas outlet. Further, manual 2-way valve V92 can be used as a purgevalve for maintenance of system 400.

In some embodiments, contactor B1 is a packed column or packed towertype contactor that is filled with tower packing in order to provide asubstantial gas-liquid contact surface as the liquid flows from the topto the bottom of the contactor.

A certain liquid level can be maintained within contactor B1. Forexample, a parallel line to contactor B1 acts as level gauge, where theliquid level is measured with capacitance meter L1. In some embodiments,contactor B1 is mainly filled with gas and the liquid level ismaintained substantially in the lower portion of contactor B1.

Capacitive liquid sensor LAH measures the liquid level inside contactorB1 and provides an alarm if it rises too high as a safety feature tohelp avoid having liquid flow into the gas outlet of contactor B1.Capacitive gas sensor LAL also measures the liquid level insidecontactor B1 and provides an alarm if the liquid level becomes too lowas a safety feature to help avoid having gas flow into the liquid outletof contactor B1.

The control module controls the liquid level and the pressure within thecontactor, measured at pressure sensors PR4 and PR10, by adjusting thewater flow via valve V6 and the transfer gas pressure at PRC5. Inparticular, pressure sensor PR10 is used for safety purposes to detectoverpressure within the contactor. In some embodiments, separator S4 ispositioned between the mixed gas supply line and pressure sensor PR4,and separator S10 is positioned between the mixed gas supply line andpressure sensor PR10.

A conductive output liquid (e.g., DI-water with NH₃ dissolved therein)having a conductivity according to the conductivity set point selectedby the user can be output from at least one liquid outlet of contactorB1 for use in semiconductor fabrication operations (e.g., rinsingoperations, wet cleaning operations). The at least one liquid outlet ofcontactor B1 can be in fluid communication with one or more liquidoutlets of system 400 by way of filter Filter 81 which can filter theconductive output liquid, and positioner POSV8, a pneumatic positioningdevice that can be used to control the flow of liquid from the systemusing continuous valve position adjustments of pneumatic 2-way valve V8.In some embodiments, system 400 includes a pump P1 to enhance thepressure of the conductive liquid output from the system.

Pneumatic 2-way valve V12 can be used as a filter drain valve formaintenance of system 400, and flow restrictors V41 and V42 can be usedto limit the flow of liquid purged from filter Filter 81. Further,pneumatic 2-way valves V13 and V20 can be used for de-aeration of filterFilter 81. Pneumatic 2-way valve V15 can be used as an additional drainfor various maintenance purposes. Pressure sensor PR8 can be used tomeasure the pressure of the conductive liquid. The controller can usethe pressure measured at pressure sensor PR8 to determine how much toadjust the pumping power of pump P1, in order to provide a constantpressure at the outlet of system 400 at dynamically-changing liquid flowrates. In some embodiments, separator S8 is positioned between theconductive liquid supply line and pressure sensor PR8.

In some embodiments, pneumatic 2-way valve V11 can be used as a centraldrain valve and pneumatic 2-way valve V15 can be used as an additionaldrain for various maintenance purposes.

The temperature of the conductive liquid output from contactor B1 can bemeasured at the outlet of the mixing device using sensor Q1, and theconductivity of the conductive liquid can be measured using sensor TR1.In some embodiments, sensor Q1 is a combined conductivity andtemperature sensor. Flow restrictor V43 can be used to limit the flow ofliquid through or by sensor Q1 and sensor TR1, and pneumatic 2-way valveV14 can be used to isolate sensor Q1 and sensor TR1 for shutdown.

As discussed above, the DI-water flow rate and conductive liquidtemperature measurements are used in conjunction with the conductivityset point to calculate the required NH₃ gas flow rate, the feed forwardcontrol that is applied in order to achieve very fast conductivitychanges upon liquid flow rate changes. In some embodiments, the NH₃ gasflow rate calculations are based on measurements of the flow rate of theconductive liquid output from contactor B1. In some embodiments, the NH₃gas flow rate calculations are based on temperature measurements of theDI-water supplied from the DI-water source. In some embodiments, astatic temperature value is used for the NH₃ gas flow rate calculations.

In some embodiments, system 400 includes capacity liquid sensor M12which is a liquid sensor that is positioned in or on a drop pan todetect water leaks. In some embodiments, system 400 includes a drain toremove liquid that has leaked into the drop pan. In some embodiments,system 400 includes pressure sensor PR18 for measuring the differentialpressure of a cabinet housing the components of system 400, and PR18generates an alarm to indicate failure modes, such as the absence ofexhaust flow from system 400. In some embodiments, system 400 usessensor Q2 as a safety monitor for monitoring the NH₃ level of thecabinet to detect NH₃ gas leaks. In some embodiments, clean dry air CDAis supplied to system 400 for operation of the pneumatically-controlledvalves. In some embodiments, system 400 includes a sniffer port that canbe used for detecting leaks in the components of system 400.

FIG. 5 is a block diagram of an exemplary gas mixing device 500according to embodiments of the technology described herein. Gas mixingdevice 500 is used for mixing NH₃ gas supplied at first inlet 520 with atransfer gas (e.g., N₂ gas) supplied at inlet 525, and outputting theresulting gas mixture via mixed gas outlet 535.

The flow rate of the transfer gas can be controlled using a mass flowcontroller or a pressure controller with a flow restrictor positionedbehind it. The flow rate of the NH₃ gas can be controlled using one ormore mass flow controllers. The example of FIG. 5 shows components of asingle mass flow controller for controlling the flow of NH₃ gas. Themass flow controller includes mass flow meter MFM 505 in fluidcommunication with inlet 520 and proportional valve 510 which is furtherin fluid communication with mixed gas outlet 535. The mass flowcontroller further includes controller 515 in electrical communicationwith MFM 505 and proportional valve 510. Controller 515 receives a setpoint 540 from another controller or processor (e.g., control module 125of FIGS. 2 and 3 ), compares it to the measured flow rate from MFM 505,and adjusts proportional valve 510 accordingly to achieve the flow ratespecified by set point 540.

Turbulent gas flows and fluctuations in pressure can result in anon-uniform mixture of NH₃ gas and the transfer gas in the gas mixingdevice. The effects of these irregularities can become more pronouncedas the length of the NH₃ gas supply line increases. Even the outlet stubof the NH₃ mass flow controller contributes to an uneven NH₃ dosage inthe gas mixture, as such a small amount of NH₃ gas is needed toinfluence the conductivity of the output liquid. For example, in atypical mass flow controller, the proportional valve is located insideof a metal body with an outlet port to connect to a gas pipe or tube.The typically short internal flow channel from the proportional valve tothe connection fitting at the outlet can still contain enough unmixedNH₃ to cause dosage fluctuations in the gas mixture, even at slightpressure changes in the system. These dosage fluctuations are unwantedin semiconductor manufacturing as they result in fluctuations in theconductivity of the liquid in the outlet of the system. It was thereforenot possible to achieve the required stability of the conductivity ofthe liquid in the outlet of the system using known configurations.

However, usage of a standard mass flow controller is preferred due tocost advantages over a custom design. The present technology isconfigured to overcome the issues described above. In some embodiments,the transfer gas is fed through a central injection tube or pipe (e.g.,injection pipe 530) directly to the opening of the proportional valveoutlet of the mass flow controller used to control the flow of NH₃ gas.The injection tube can be mounted in a t-fitting with an openingpositioned such that the mixing point of the transfer gas with the NH₃is moved from the far end of the connection fitting to substantially ator near the internal outlet of the mass flow controller proportionalvalve. In some embodiments, the opening of the transfer gas injectiontube is approximately 5 to 10 mm from the internal outlet of the massflow controller proportional valve. This measure can reduce the pure(e.g. unmixed) NH₃ gas volume in the system, and therefore reduce oreliminate the influence that fluctuations in the internal pressure ofthe contactor has on the stability of the conductivity of the liquid inthe outlet of the system. At the same time, standard mass flowcontrollers can still be used in the system, providing an economicadvantage.

The required flow rate of the NH₃ gas in the system is comparativelysmall. For example, in a typical system with a liquid flow range from0.5 L/min to 32 L/min at a given temperature with a conductivity setpoint between 5 μS/cm and 40 μS/cm, the NH₃ gas flow can be between 0.48sccm and 1197 sccm. In certain cases, higher flow and conductivityranges are used with a flow rate, for example, a liquid flow rate of 48L/min and a conductivity set point of up to 200 μS/cm, which requires aNH₃ gas flow of about 41.1 slm. Nevertheless, the required gas flowrange can span at least three magnitudes for some exemplaryapplications, which cannot be covered by a single mass flow controllerwhich typically can cover a flow range of one- to one-and-a-halfmagnitudes.

In some embodiments, the gas mixing device includes a plurality of massflow controllers to cover a large range of required NH₃ gas flows. FIG.6 is a block diagram of an exemplary gas mixing device 600 according toembodiments of the technology described herein. Gas mixing device 600 isused for mixing NH₃ gas supplied at first inlet 620 with the transfergas (e.g., N₂ gas) supplied at inlet 625, and outputting the resultinggas mixture via mixed gas outlet 635. Gas mixing device 600 includesthree mass flow controllers (MFC1-MFC3), and inlet valves V601-V603 tosupply the NH₃ gas to MFC1-MFC3, respectively. Filter 640 can be used tofilter the mixed gas prior to being provided to the contactor. Pressurerelief valve V604 can be used as a safety device to relieve pressurebuildup in the supply line before catastrophic system failure.

Although FIG. 6 shows three mass flow controllers, one of ordinary skillin the art would appreciate that fewer or more mass flow controllers canbe used without departing from the spirit and the scope of thetechnology.

Each of mass flow controllers MFC1-MFC3 is equipped with a centralinjection tube similar to injection pipe 530 of FIG. 5 for injecting theflow of transfer gas substantially at or near the internal outlet ofeach mass flow controller's proportional valve (not shown). Accordingly,the full flow of the transfer gas can be applied to all mass flowcontrollers used to feed NH₃ into the transfer gas. During operation,the flow of the transfer gas is varied in response to the measuredliquid flow rate, in order to account for the solubility of the transfergas in the water. In some embodiments, the transfer gas is controlled inresponse to the flow of the NH₃ gas to act as a buffer between the NH₃and the DI-water. The flow rate of the transfer gas is also used tomaintain the liquid level inside of the contactor.

In some embodiments, the gas mixing device includes one or more fastswitching valves instead of one or more mass flow controllers to controlthe NH₃ gas flow. Because fast switching valves can have switching timesin the millisecond range or below, a nearly continuous flow of NH₃ gascan be supplied to the system. The switching valves are arranged in suchway that there is no large NH₃ gas volume downstream of the switchingvalves. In some embodiments, this is achieved with an injection tube forsupplying the transfer gas directly to the valve closures.

FIG. 7 is a flow diagram of a method 700 for dissolving NH₃ gas inDI-water, according to embodiments of the technology described herein.NH₃ gas can be supplied (705) to a first inlet of a gas mixing device.As described above, the gas mixing device can have a first inlet influid communication with a first gas source for supplying NH₃ gas to thegas mixing device. A transfer gas can be supplied (710) to a secondinlet of the gas mixing device. For example, the gas mixing device canhave a second inlet in fluid communication with a second gas source forsupplying a transfer gas to the gas mixing device.

The NH₃ gas and the transfer gas can be mixed within the gas mixingdevice to create a gas mixture. The gas mixture comprising the NH₃ gasand the transfer gas from the gas mixing device and DI-water can besupplied (715) to a contactor. In some embodiments, the gas mixingdevice includes a mixed gas outlet that is in fluid communication with agas inlet of the contactor, and the DI-water is in fluid communicationwith a liquid inlet of the contactor.

In some embodiments, the gas mixture is provided to the DI-water supplyline upstream of the contactor. For example, the mixed gas outlet of thegas mixing device can be in fluid communication with the DI-water supplyline at a location upstream of an inlet substantially at or near the topof the contactor. This configuration is advantageous because asubstantial portion of the NH₃ gas can be dissolved in the DI-waterprior to entering the contactor where the remaining NH₃ gas can bedissolved. To further enhance this effect, a static mixer can bepositioned in-line with the DI-water supply downstream of the locationwhere the gas mixture is provided to the DI-water supply line, butupstream of the contactor inlet.

The flow rate of the DI-water can be measured (720), and a flow rate ofthe NH₃ gas can be set (725) based on the measured flow rate of theDI-water and a predetermined conductivity set point. For example, asdescribed above, a control module in the system can set the requireddosage of NH₃ gas to provide to the gas mixing device based oncalculations using a measurement of the DI-water flow rate and aconductivity set point (e.g., Kappa) provided by the user to indicatethe desired conductivity of the resulting conductive liquid that isoutput from the system. The required flow rate of NH₃ gas can beproportional to the desired DI-water flow rate and/or conductivity ofthe resulting conductive liquid. In some embodiments, the NH₃ flow ratecalculations are based on a flow rate measurement of the conductiveliquid output instead of the DI-water flow rate.

As described in detail above, the calculation of the required flow rateor dosage of NH₃ gas to supply can be based on predetermined assumptionsabout the temperature range of the liquid in the system withoutrequiring an actual temperature measurement to be obtained. This canprovide certain advantages such as lower up front equipment complexityand cost, as well as lower cost of ownership from not having to maintainthe additional components that would be required for making temperaturemeasurements. Further, development time of the system software can bereduced with fewer active components to integrate, and processing timescan be reduced as no processing cycles are dedicated to obtaining thetemperature measurement, and the temperature value used for thecalculations can be static.

In some embodiments, a temperature sensor is positioned at or near aninlet of the contactor for sensing or measuring the temperature of theDI-water (or the DI-water and gas mixture) entering the contactor. Insome embodiments, a temperature sensor is positioned at or near anoutlet of the contactor for sensing or measuring the temperature of theconductive liquid (e.g., DI-water with NH₃ gas dissolved therein) thatis output from the contactor. The control module can be in communicationwith the one or more temperature sensors, and can periodically orconstantly receive sensor output signals indicating the temperature ofthe liquid.

The temperature measurements can be used for applications that requiregreater accuracy of the conductivity of the resulting conductive liquid.For example, instead of using an assumed or static liquid temperaturevalue for calculations of the required NH₃ gas flow rate, the controlmodule can perform its calculations using a measurement of the actualtemperature of the liquid in addition to the measurement of the DI-waterflow rate and the conductivity set point provided by the user.

The DI-water having NH₃ gas dissolved therein can be flowed (730) fromthe contactor. In some embodiments, the DI-water having NH₃ gasdissolved therein flows from a liquid outlet of the contactor and exitsthe system for use in a wet cleaning operation. In some embodiments, thesystem includes a pump downstream of the contactor outlet for enhancingthe pressure of the conductive liquid supplied by the system.

FIG. 8 is a graph of the performance of an exemplary system forgenerating and delivering a conductive liquid comprising DI-water withNH₃ gas dissolved therein. The exemplary system is designed with a gasinlet at the bottom of a tower packing column, which is the typicalconfiguration for such a system. FIG. 8 includes a curve 820corresponding to the conductivity of the liquid output from thecontactor in μS/cm overlaid with a curve 810 indicating the flow rate ofliquid in the system in L/min measured over the course of 50 minutes ofsystem operation with a conductivity set point of 10 μS/cm.

During operation of the system, the liquid flow rate was increased ordecreased periodically while conductivity of the output liquid wasmeasured. As shown in FIG. 8 , the conductivity of the output liquidgenerally fluctuates less than 5 μS/cm from the set point, with largermomentary deviations following a change in the liquid flow rate, anddeviation 830 being the largest observed deviation of approximately 10μS/cm from the set point.

FIG. 9 is a graph of the performance of an exemplary system forgenerating and delivering a conductive liquid comprising DI-water withNH₃ gas dissolved therein. The system corresponding to the graph of FIG.9 includes optimizations described herein (e.g., FIGS. 4 and 5 ) such assupplying the mixed gas outlet to the DI-water supply line upstream ofthe contactor inlet.

FIG. 9 includes a curve 920 corresponding to the conductivity of theliquid output from the contactor in μS/cm overlaid with a curve 910indicating the flow rate of liquid in the system in L/min measured overthe course of 120 minutes of system operation with a conductivity setpoint of 10 μS/cm.

During operation of the system, the liquid flow rate was increased ordecreased periodically while conductivity of the output liquid wasmeasured. As shown in FIG. 9 , the conductivity of the output liquidgenerally fluctuates less than 1 μS/cm from the set point, with onlysmall brief momentary deviations of 1 μS/cm or less following a changein the liquid flow rate.

Accordingly, as demonstrated, the present technology can maintain aprecise control of the output liquid conductivity over a substantiallyhigher range of liquid flow than existing systems. The applied controlsystem only feeds the required NH₃ gas into the system, without anyexcess, providing an economic advantage over existing systems. Further,due to the direct contact between gas and DI-water, the NH₃ absorptionin the water is nearly 100%. For a typical conductivity set point forthe supplied liquid of, for example, 40 μS/cm, ammonium is notdetectable in the off gas, resulting in a much lower risk of NH₃contamination of the ambient than existing systems.

Further, solutions of NH₃ can exhibit an etching behavior to silicon.For certain semiconductor processes, such as treatment of advancedtransistor structures (e.g., finFETs), a defined but only very smalletching capability is required. Defined dilute NH₃ solutions can havethe required etching capability at a certain NH₃ concentrations, but itis critical to tightly control the applied NH₃ concentration so as notto etch away more than is required. Accordingly, the technologydescribed herein provides a solution for semiconductor processes fortreatment of advanced transistor structures.

The etching capability of NH₃ solutions is additionally modified by theoxygen content of the solution. Certain semiconductor applications needa low oxygen content in the NH₃ solution. This is difficult to achieveby dilution of concentrated NH₃, which is typically oxygen saturated dueto a long storage time. Degassing of such a solution is difficult, asunder such conditions NH₃ is typically also stripped form the solution.Accordingly, generation of a dilute NH₃ solution out of NH₃ gas andDI-water according to the techniques described herein overcomes thisproblem, as the DI-water can be degassed with conventional techniquesand pure NH₃ gas only contains insignificant traces of oxygen.

Cobalt is replacing materials such as tungsten in the fabrication of newsemiconductor devices such as finFETs. According to a Pourbaix diagramfor cobalt in an aqueous solution, below a pH of 9 cobalt has thepotential to form a corrosive ion (Co²⁺). With a typical pH value lessthan 6, DI-water can thermodynamically corrode cobalt. Thus, rinsingwith DI-water as is typically done in the last step of fabrication, willattack the metal, starting from cracks in the surface down tosignificant material loss. Homeopathic addition of NH₄OH has been foundto act as inhibitor and stop this corrosion simply by shifting the pH ofDI-water. Conversely, higher concentrations of NH₄OH have been found todissolve the Co(OH)₂ with [Co(NH₃)₄]²⁺ complexes, which again increasethe risk of galvanic corrosion.

It is therefore important to control the pH of the liquid solution in atight region. As there is a correlation between the pH of a liquid andits conductivity, a reliable control method is to control theconductivity of the NH₃ solution. Accordingly, the technology describedherein likewise provides a solution for control of pH in solutions usedfor semiconductor processes for treatment of advanced transistorstructures.

Variations, modifications, and other implementations of what isdescribed herein will occur to those of ordinary skill in the artwithout departing from the spirit and the scope of the invention.Accordingly, the invention is not to be limited only to the precedingillustrative descriptions.

What is claimed is:
 1. A system for dissolving ammonia gas in DI-water,the system comprising: a deionized water source; a gas mixing devicecomprising: a first inlet in fluid communication with a first gas sourcefor supplying ammonia gas; a second inlet in fluid communication with asecond gas source for supplying a transfer gas; a mixed gas outlet foroutputting a gas mixture comprising the ammonia gas and the transfergas; at least one flow control device in fluid communication with thefirst inlet of the gas mixing device to control a flow of the ammoniagas; and a gas injector in communication with the second inlet, the gasinjector being positioned within the gas mixing device to direct a flowof the transfer gas to an opening of an outlet of the at least one flowcontrol device within the gas mixing device; a contactor in fluidcommunication with the deionized water source and the mixed gas outletvia at least one inlet of the contactor, the contactor generatingdeionized water having ammonia gas dissolved therein; a sensor in fluidcommunication with the at least one inlet of the contactor for measuringa flow rate of the deionized water; and a controller in communicationwith the sensor, the controller configured to adjust a pressure of thetransfer gas output from the second gas source based on the flow rate ofthe deionized water measured by the sensor.
 2. The system of claim 1wherein the mixed gas outlet is in fluid communication with thedeionized water source upstream of the at least one inlet of thecontactor.
 3. The system of claim 2 further comprising a static mixingdevice positioned upstream of the at least one inlet of the contactor,the static mixing device for mixing the gas mixture output from the gasmixing device with deionized water output from the deionized watersource.
 4. The system of claim 1 wherein the contactor is a packedcolumn or packed tower type contactor.
 5. The system of claim 1 whereinthe at least one outlet of the contactor comprises: a gas outlet forexpelling an off gas from the contactor; and a liquid outlet foroutputting the deionized water having ammonia gas dissolved therein. 6.The system of claim 1 further comprising a fluid level sensor in fluidcommunication with the top and the bottom of the contactor.
 7. Thesystem of claim 1 further comprising a pressure sensor in fluidcommunication with the contactor.
 8. The system of claim 1 furthercomprising a temperature sensor in fluid communication with one of: theat least one inlet of the contactor for measuring a temperature of thedeionized water; and at least one outlet of the contactor for measuringa temperature of the deionized water having ammonia gas dissolvedtherein.
 9. The system of claim 8 further comprising a controller incommunication with the sensor and the temperature sensor, the controllerconfigured to set a flow rate of the ammonia gas supplied from the firstgas source based on at least one of a temperature measured by thetemperature sensor, the flow rate of the deionized water measured by thesensor or a predetermined conductivity set point.
 10. The system ofclaim 1 further comprising a pump in fluid communication with the atleast one liquid outlet of the contactor.
 11. The system of claim 1wherein the mixed gas outlet is in fluid communication with thedeionized water source.
 12. The system of claim 1 wherein the at leastone inlet of the contactor comprises: a liquid inlet in fluidcommunication with the deionized water source; and a gas inlet in fluidcommunication with the mixed gas outlet.
 13. The system of claim 12wherein the gas inlet comprises an exit orifice within the contactorthat is positioned substantially at a mean level of a liquid in thecontactor.
 14. A method for dissolving ammonia gas in deionized water,the method comprising: supplying ammonia gas to a first inlet of a gasmixing device; controlling a flow rate of the ammonia gas supplied tothe gas mixing device with at least one flow control device; supplying atransfer gas to a second inlet of the gas mixing device; directing aflow of the transfer gas within the gas mixing device to an opening ofan outlet of the at least one flow control device of the gas mixingdevice; supplying a gas mixture comprising the ammonia gas and thetransfer gas from the gas mixing device and deionized water to acontactor; measuring a flow rate of the deionized water; flowing thedeionized water having ammonia gas dissolved therein from the contactor;and adjusting a pressure of the transfer gas based on the flow rate ofthe deionized water.
 15. The method of claim 14 further comprisingmixing the gas mixture output from the gas mixing device with thedeionized water upstream of the contactor.
 16. The method of claim 14wherein the contactor is a packed column or packed tower type contactor.17. The method of claim 14 further comprising: expelling an off gas froma gas outlet of the contactor; and flowing the deionized water havingammonia gas dissolved therein from a liquid outlet of the contactor. 18.The method of claim 14 further comprising sensing a fluid level of fluidin the contactor.
 19. The method of claim 14 further comprising sensinga fluid pressure of fluid in the contactor.
 20. The method of claim 14further comprising sensing a temperature of at least one of: (i) thedeionized water, and (ii) the deionized water having ammonia gasdissolved therein.
 21. The method of claim 20 further comprising settinga flow rate of the ammonia gas to supply based on at least one of thetemperature, the flow rate of the deionized water or a predeterminedconductivity set point.
 22. The method of claim 14 wherein flowingfurther comprises pumping the deionized water having ammonia gasdissolved therein from the contactor via a liquid outlet of thecontactor.
 23. The method of claim 14 wherein supplying the gas mixtureto the contactor further comprises supplying the gas mixture to a gasinlet of the contactor, wherein the gas inlet comprises an exit orificewithin the contactor that is positioned substantially at a mean level ofa liquid in the contactor.